Mid and deep-UV antireflection coatings and methods for use thereof

ABSTRACT

An antireflective coating composition for use with chemically amplified photoresist compositions comprising a polymer composition which is highly absorbent to mid and deep UV radiation, which is substantially inert to contact reactions with a chemically amplified photoresist composition, and which is insoluble in the developer for the chemically amplified photoresist composition.

RELATED APPLICATION

This application is a division of U.S. patent application Ser. No.08/017,939, filed Feb. 16, 1993, now U.S. Pat. No. 5,401,614 which is acontinuation-in-part of U.S. patent application Ser. No. 07/845,404,filed Mar. 3, 1992, entitled "Mid and Deep UV Antireflection Coatingsand Methods for Use Thereof" abandoned.

FIELD OF INVENTION

The present invention is directed to antireflective coating compositionsfor use with chemically amplified photoresist compositions. Moreparticularly, the invention is directed to film forming compositionswhich are highly absorbent to mid and/or deep UV radiation and which areinsoluble in the chemically amplified photoresist compositions and thedevelopers therefor. The invention also provides methods for formingphotoresist images having improved linewidth control.

BACKGROUND

As semiconductor manufacturers have sought to be able to fabricatedevices having a higher degree of circuit integration to improve deviceperformance, it has become necessary to use photolithographic techniquesusing shorter wavelengths in the mid and deep UV spectra to achieve finefeatures. In the process of making the desired very fine patterns manyoptical effects are experienced which lead to distortion or displacementof images in the photoresist that are directly responsible for wiringline width variations, opens and shorts, all of which can lead todeteriorated device performance. Many of these optical effects areattributable to substrate geometry and reflectivity influences thatinclude halation and other reflected light scattering effects which maybe due to uneven topography or the varying (wavelength dependent)reflectivity of the substrates and wires or layers being patternedthereon to define the desired features. Such effects are furtherexacerbated by both the non-uniformity of the photoresist film and filmthickness. These effects are manifested in lithographic patterns unevenline width, often with "reflective notching", due to standing wavephenomena, non-vertical pattern sidewalls.

U.S. Pat. No. 4,910,122 to Arnold et al. is directed to processes forovercoming the reflectivity problems experienced in thin filmlithography used in the fabrication of circuits of increasing density orintegration. The process uses an antireflective film compositioncomprising a polymer having low surface energy (and which mayincorporate a dye compound) as a layer interposed between the substrateand the imaging layer which reduces the dilatory reflective effects andwhich is removable by the photoresist developer.

It has been discovered that such processes are not compatible withchemically amplified resist compositions. Chemically amplifiedphotoresist compositions are those in which the reaction continuesthrough a mechanism that involves image formation of photoacidproduction and secondary acid production affects. An example of suchcomposition is found in U.S. Pat. No. 4,491,628 to Ito et al. Thecodevelopable antireflective coatings adversely react with thecomponents of the photoresist.

SUMMARY OF THE INVENTION

The present invention provides an antireflective coating composition foruse with chemically amplified photoresist compositions comprising apolymer composition which is highly absorbent to mid and/or deep UVradiation, and which is substantially inert to contact reactions with achemically amplified photoresist composition, and which is insoluble inthe developer for the chemically amplified photoresist composition.

The polymeric composition used in the antireflective coating is selectedfrom the group consisting of polysilanes which strongly absorbultraviolet radiation having one or more wavelengths in the mid and/ordeep UV region, polyvinyl aromatic compositions which strongly absorbradiation having one or more wavelengths in the deep UV region,pre-imidized polyimides which strongly absorb radiation having one ormore wavelengths in the deep UV region, and polyaryl ethers whichstrongly absorb radiation having one or more wavelengths in the deep UVregion. The polymers of the composition are further characterized asable to form a discrete underlayer, are immiscible with the photoresist,and are not removable during normal wet development of the photoresist.The pre-imidized polyimides are further characterized as insoluble inaqueous alkaline photoresist developer solutions, and soluble in organicsolvents which are not used in the overlaying photoresist composition.The polyvinyl aromatic composition may further be characterized aseither cross-linkable or, in the alternative, not cross-linkable, andwhere such polyvinyl aromatic composition is cross-linkable, thecompositions may be cross-linked by processing or alternatively may notbe cross-linked during processing. In order to effectively protectagainst image distortion, the antireflective coating should have a highoptical density at the exposing wavelength. Preferably, the opticaldensity should be at least 0.25 at each wavelength for which the resistis sensitive and corresponding to each particular wavelength of theexposing light. Since relatively thin coatings contribute to the ease inrunning an uncomplicated process, it is preferred to employ materialexhibiting an optical density of at least 2.0/μm to overcomelithographic variations due to reflectivity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A, 1B, and 1C are cross sectional views of hypotheticalphotoresist relief images showing ideal images, additive defects, andsubtractive defects.

FIG. 2 is a graph showing a comparison of line width variations ofcompositions with and without the antireflective coating compositions ofthe invention.

FIGS. 3A and 3B are scanning electron micrographs showing partialperspective views of photoresist lines and spaces after processing withand without the antireflective coating compositions of the invention.

FIG. 4 is a graph showing reflectance as a function of photoresistthickness with and without the antireflective coating compositions ofthe invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

According to the invention, antireflective coating compositions areprovided for use with chemically amplified photoresist compositions.These polymer compositions are characterized by being highly absorbentto mid and deep UV radiation, by being substantially inert to contactreactions with a chemically amplified photoresist composition, and bybeing substantially insoluble in the developer for the chemicallyamplified photoresist composition.

The polymeric composition used in the antireflective coating is selectedfrom the group consisting of polysilanes which strongly absorbultraviolet radiation having one or more wavelengths in the mid and/ordeep UV region, polyvinyl aromatic compositions which strongly absorbradiation having one or more wavelengths in the deep UV region,pre-imidized polyimides which are insoluble in aqueous alkalinephotoresist developer solutions, and which polyimides strongly absorbradiation having one or more wavelengths in the deep UV region, andpolyaryl ethers which strongly absorb radiation having one or morewavelengths in the deep UV region. The polymers of the composition areadditionally characterized as capable of forming a discrete underlayer,are immiscible with the photoresist, and are not removable during normalwet development of the photoresist. The pre-imidized polyimides arefurther characterized as insoluble in aqueous alkaline photoresistdeveloper solutions, and soluble in organic solvents which are not usedin the overlaying photoresist composition. Preferred pre-imidizedpolyimides are soluble in a solvent selected from the group consistingof cyclohexanone, cyclopentanone, dioxane, gamma butyrolactone, andtetrahydrofuran, and are insoluble in one of acetate esters orpropionate esters or lactate esters. In order to effectively protectagainst image distortion, the antireflective film should have a highoptical density at the exposing wavelength. Preferably, the absoluteoptical density should be at least 0.25 at each wavelength for which theresist is sensitive and corresponding to each particular wavelength ofthe exposing light. In a preferred embodiment of the present inventionfor a deep UV lithographic process, the antireflective film should havean absolute optical density of at least 0.25 through the range ofwavelengths from 235 to 280 nm. Such thin films are easy to apply, donot adversely affect such exposure parameters as depth of focus,exposure dose, and process latitude, and may be facilely removed afterprocessing. Use of the compositions of the invention in a lithographicprocess is particularly advantageous in relaxing the requirement forstrict control of the photoresist coating thickness. The films mayremain in the structure or may alternatively be removed depending uponthe requirements of subsequent processes or upon the requirements of thedevice ultimately produced.

It has been found that lithographic patterns are substantially improvedby the incorporation of the mid and/or deep UV antireflective coating ofthe present invention into a lithographic process. Without an underlyingantireflective film, linewidth variations arise in the imaged anddeveloped resist over underlying reflective features having uneventopography. The variations are due to the non-uniform coupling of lightinto the photoresist film resulting from the dependence of the standingwave contribution on the localized thickness of the resist. With anunderlying antireflective film, reflected light is minimized by theabsorbance of incident light by the antireflective coating. Standingwaves are diminished and the lithographic pattern profiles obtained areessentially vertical. Neither the "feet" (protrusions from the bottom ofthe sidewalls of each line into the space between lines) which areotherwise observed in conventional lithography, nor the "flairs" (anon-vertical sidewall or a severe foot) which are otherwise observedwith low surface energy polymer coatings, are detected in processespracticed with the present invention.

It has also been unexpectedly discovered that the antireflectivecompositions of the invention do not admix with nor form an interfaciallayer with many chemically amplified resists. Interfacial layers aretransitional regions between two polymeric layers wherein theinterfacial layers have compositions characterized by the presence ofspecies from each adjoining layer. Interfacial layers are typicallyundesirable. It is presumed that the antireflective compositions of thepresent invention demonstrate these beneficial properties as a result ofthe low solubility or insolubility of the components of theantireflective film in the solvents used for the chemically amplifiedphotoresists and also as a result of the immiscibility of theantireflective layer components in the photoresist composition.

Furthermore, it has also been surprisingly found that the antireflectivecompositions of the present invention do not adversely affect thesensitivity of the overlying chemically amplified photoresist, noradversely affect the lower sidewall profile in the processed reliefimage. Certain chemically amplified photoresists may exhibit anincrease, or less commonly a decrease, in the required dose of exposingradiation for patterning after contact with, or exposure to, certaindeleterious chemical species. Where such deleterious species are presentin the film underlaying the chemically amplified resist,desensitization, or hypersensitization, of the chemically amplifiedresist takes place by means of a contact reaction with the filmcontaining the deleterious species. The contact reaction may be limitedto the interfacial region, or may be exacerbated by means of diffusionof the deleterious species into the chemically amplified resist film.

The lithographic result of a contact reaction is easily understood byreference to FIGS. 1A, 1B, and 1C. Referring to FIG. 1A, arepresentation of an ideal photoresist relief image over anantireflective layer is shown. In FIG. 1A, lines of resist (2) are shownoverlaying an antireflective layer (5), said antireflective layer beingcoated on a substrate (6). The sidewalls (2a) are vertical, and no footor scum is present in the space (8). Referring to FIG. 1B, an additivedefect in the photoresist relief image is shown, which is understood tomean that additional unwanted resist material is present afterdevelopment. In FIG. 1B, lines of resist (1) are shown overlaying anantireflective layer (5), said antireflective layer being coated on asubstrate (6). The sidewalls (1a) are not vertical, and a foot ispresent. In severe cases, the bottom of space (7) may remain unopenedafter development. Referring to FIG. 1C, a subtractive defect in thephotoresist relief image is shown, which is understood to mean thatresist material has been undesirably removed after development. In FIG.1C, lines of resist (3) are shown overlaying an antireflective layer(5), said antireflective layer being coated on a substrate (6). Thesidewalls (3a) are not vertical, exhibiting a notching at the bottom ofthe line (3). In severe cases, the line may be entirely lost during thedevelopment process.

In a positive tone, acid amplified photoresist, where the deleteriousspecies emanating from the underlying film is basic in nature, thecontact reaction is manifested by the formation of an additive defect asshown in FIG. 1B. In order to compensate for the defect, the exposuredose is increased, and the resist is deemed to be desensitized. In anegative tone, acid amplified photoresist, where the deleterious speciesis basic in nature, the contact reaction is manifested by the formationof a subtractive defect as shown in FIG. 1C, the exposure doserequirement is increased, and the resist is deemed desensitized. As thepractitioner will understand, the character of the observed defects arereversed for an acid amplified photoresist where the deleterious speciesis acidic in nature, resulting in a decreased exposure doserequirement., or hypersensitivity. Similarly, where the chemicallyamplified resist involves photogenerated base catalysis, the presence ofa deleterious acidic species ultimately leads to desensitization, and abasic species leads to hypersensitization.

Another unexpectedly advantageous property of the present invention isthat the catalytic component of an exposed and undeveloped chemicallyamplified photoresist does not exhibit diffusion into the underlayingantireflective composition, another example of an adverse contactreaction. It is known in the art that the mobile acid moiety which isgenerated by radiation absorbed by many chemically amplifiedphotoresists and which is necessary for catalyzing the reactions leadingto differential solubility of the resists is capable of diffusing awayfrom the vicinity where such acid is generated. see, L. Schlegel, T.Ueno, H. Hayashi, and T. Iwayanagi, J. Vac. Sci. Technol., B9, 278(1991). Diffusion of the acid moiety from such an acid amplified resistinto an adjacent antireflective layer will cause decreased photoresistsensitivity, resulting in an additive defect in a positive tone process.Such decreased sensitivity is seen when acid catalyzed chemicallyamplified photoresists are used in conjunction with antireflectivelayers having compositions comprising nitrogen containing solvents asare known in the art, however the compositions of the present inventiondemonstrate unexpectedly improved performance.

Diffusion of the catalytic moiety is particularly severe when theunderlaying antireflective layer comprises plasticizers or residualsolvents, or is characterized by having relatively large, interconnectedinterstitial spaces within the polymer matrix. Thus, in an alternativeembodiment of the present invention, it may be advantageous, but is notrequired, that the solvent be removed from the antireflectivecompositions after spin casting. In yet another alternative embodimentof the present invention, the polymer is processed by heating to atemperature above the glass transition temperature to drive residualsolvent from the polymer matrix and to anneal the matrix.

As an additional unexpected benefit, the antireflective coating of thepresent invention provides a chemical barrier between the chemicallyamplified photoresist and the substrate. The chemical barrier propertiesare important when processing chemically amplified photoresistsdeposited over silicon, or over certain less reflective materials suchas titanium nitride (TIN), silicon nitride (Si₃ N₄), and TEOS, which ischemical vapor deposited silicon from tetraethyl orthosilicate. Thesurfaces of such materials are extremely sensitive to environmentalinfluences, and may have an acidic or basic surface character as aresult of deposition conditions, exposure to air or water, cleaning inacidic or basic solutions prior to photoresist application, retention ofcontaminants from a previous processing step, or as an intrinsicproperty of the material. For example, it is known that the cleaning ofsubstrates having a silicon comprising surface layer in strong acidswill result in an acidic surface characteristic. Similarly, the exposureof TiN to bases or the incorporation of hydrogen will give rise to abasic surface characteristic. Such acidic or basic surfaces may giverise to adverse contact reactions, and the antireflective coating of theinvention functions as a barrier layer to provide quite usefulprotection against environmental contaminants which results in extendedprocess latitude.

EXAMPLE 1

A mixture of cyclohexylmethyldichlorosilane (54.75 g, 0.277 mol) anddiphenyldichlorosilane (17.55 g, 0.069 mol) was added rapidly todispersed sodium (45.4 g, 40% mineral oil, 0.79 mol) in a refluxingmixture of toluene (375 ml) and diglyme (40 ml). After the addition, themixture was refluxed for one hour and allowed to cool to roomtemperature. At this point, isopropyl alcohol (75 ml) was added slowlyto quench any unreacted sodium and the copolymer formed was precipitatedinto isopropyl alcohol (2 l). The solid was gravity filtered, air driedand extracted with toluene (500 ml). The toluene extract was washed withwater (3×250 ml) and dried over anhydrous sodium sulfate. Evaporation ofthe solvent gave 10.24 grams of copolymer:poly(cyclohexylmethylsilane-co-diphenylsilane) having an optical densityof 2.4/μm.

The copolymer was dissolved in toluene to form a 10% by weight solution.After filtration, a thin film of the copolymer was deposited on thesurface of a silicon wafer by spin casting at 3000 rpm for 30 seconds.The coated wafer was soft-baked at 90° C. for 60 seconds leaving a filmof 0.3 μm thickness exhibiting an optical density at 248 nm of 0.72.

A deep- UV chemically amplified photoresist comprising a partiallyt-butyloxycarbonyloxy substituted poly(p-hydroxystyrene) i.e.,poly(p-hydroxystyrene-co-p-t-butyloxycarbonyloxy-styrene) and aphotoacid generator,trifluoromethyl-sulfonyloxybicyclo[2.2.1]-hept-5-ene-2,3-dicarboximidein a casting solvent propylene glycolmonomethyl ether acetate (PMacetate) was applied as a 1.0 μm thick film to the surface of thesilicon wafer, which had been coated with the antireflection material,by spin casting at 3200 rpm for 30 seconds, followed by a 90° C./60second soft-bake. The antireflective material and photoresist coatedwafer was then exposed to the output of a KrF laser (5 Mj/cm²) throughsuitable optics and reticle. The exposed wafer was baked at 90° C. for90 seconds, allowed to cool and finally developed by immersion in 0.24Ntetramethylammonium hydroxide (TMAH) / water solution.

The development removed the photoresist composition, but not theantireflective layer. The pattern may be further transferred through theantireflective layer to the substrate using CF₄ reactive ion etch (RIE).

EXAMPLE 2

A crosslinkable poly(cyclotetramethylenesilane) made using the synthesisprovided by R. West in J. Organomet. Chem., 300, 327 (1986) was coatedonto silicon wafers to a thickness of about 2.0 μm as was done with theantireflective coating of Example 1.

Thereafter, the treated wafer was overcoated with the deep UVphotoresist composition as set forth in Example 1 to a thickness ofabout 1.0 μm. The photoresist was imaged using a KrF laser and isdeveloped with 0.24N TMAH. The image was transferred through theantireflective coating with CF₄ RIE.

EXAMPLE 3

Poly(2-vinylnaphthalene), 2.0 grams, available commercially (AldrichChemical: 19,193-0; Monomer-Polymer:7668) was dissolved in xylene (98grams). The solution was cast upon a bare silicon wafer at a spin speedof 2400 rpm for 30 seconds. The coated wafer was then baked at 90° C.for 60 seconds yielding polymeric film with a thickness of 0.05 μmexhibiting an optical density at 248 nm of 0.26.

The deep UV chemically amplified photoresist composition of Example 1was applied over the antireflective layer on the silicon wafer as a 1.0μm thick coating in the manner described in Example 1. The coated waferwas imaged with a KrF laser (5mJ/cm²), subjected to a post exposure bake(PEB) at 90° C. for 90 seconds, and developed by immersion in 0.24NTMAH. The pattern was further transferred through the antireflectivecoating with O₂ RIE. There was some evidence of undercutting of theimage profiles.

EXAMPLE 4

Poly(2-vinylnaphthalene) having an optical density of about 5.2/μm, 1.76grams, available commercially (Aldrich Chemical: 19,193-0;Monomer-Polymer 7668), and 240 mg of2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (DABMC, a thermallylabile cross-linking agent) were added to 98 grams of xylene. Thesolution, upon spin coating on a silicon wafer at 2400 rpm, yielded apolymeric film with a thickness of 0.05 μm. The coated wafer was thenhard-baked at 180° C. for 90 seconds to yield a cross-linked polymericfilm with an optical density at 248 nm of 0.26.

The deep UV chemically amplified photoresist composition of Example 1was applied to the antireflective coated silicon wafer as a 1.0 μm thickcoating in the manner described in Example 1. The coated wafer wasimaged with a KrF laser (5mJ/cm²), subjected to a post exposure bake(PEB) at 90° C. for 90 seconds, and developed by immersion in 0.24NTMAH. The pattern was further transferred through the antireflectivecoating with O₂ RIE.

EXAMPLE 5

A solution comprised of 0.93 grams poly-(2-vinyl-naphthalene), 0.07grams 2,6-bis(4-azido-benzylidene)-4-phenylcyclohexanone (DABPC) and 49grams xylene was prepared and filtered to 0.2 μm. The solution was caston a spinning silicon wafer (2400 rpm for 30 seconds). The coated waferwas baked at 180° C. for 90 seconds leaving a 0.05 μm thick crosslinkedfilm exhibiting an optical density at 248 nm of 0.27.

The deep UV chemically amplified photoresist composition of Example 1was applied to the antireflective coated silicon wafer as a 1.0 μm thickcoating in the manner described in Example 1. The coated wafer wasimaged with a KrF laser (5mJ/cm²), subjected to a post exposure bake(PEB) at 90° C. for 90 seconds, and developed by immersion in 0.24NTMAH. The pattern was further transferred through the antireflectivecoating with O₂ RIE.

EXAMPLE 6

Poly(1-vinylnaphthalene) was purchased commercially (Monomer-Polymer:8170). A 4% solids solution was prepared by adding 1.8 grams polymer and0.2 grams DABMC to 48 grams xylene. Spin coating on a bare silicon waferat 3000 rpm followed by a post apply bake at 180° C. for 90 secondsresulted in a 0.1 μm thick film with an optical density at 248 nm of0.5.

The deep UV chemically amplified photoresist composition of Example 1was applied to the antireflective coated silicon wafer as a 1.0 μm thickcoating in the manner described in Example 1. The coated wafer wasimaged with a KrF laser (5mJ/cm²), subjected to a post exposure bake(PEB) at 90° C. for 90 seconds, and developed by immersion in 0.24NTMAH. The pattern was further transferred through the antireflectivecoating with O₂ RIE.

EXAMPLE 7

Poly(acenaphthylene) is commercially available from Monomer-Polymer(8675). A 4% solution in xylene yields, upon spin casting at 3000 rpmand soft-baking at 90° C. for 60 seconds, a 0.1 μm film with an opticaldensity at 248 nm of 0.6.

The deep UV chemically amplified photoresist composition of Example 1was applied to the antireflective coated silicon wafer as a 1.0 μm thickcoating in the manner described in Example 1. The coated wafer wasimaged with a KrF laser (5mJ/cm²), subjected to a post exposure bake(PEB) at 90° C. for 90 seconds, and developed by immersion in 0.24NTMAH. The pattern was further transferred through the antireflectivecoating with O₂ RIE.

EXAMPLE 8

Poly(4-vinylbiphenyl) is commercially available from Aldrich Chemical(18,254-0). To 95 grams of xylene were added 0.6 grams DABPC and 4.4grams polymer. After filtration a thin film of the polymeric mixture wasdeposited on a silicon wafer by spin coating at 4000 rpm for 30 seconds.The coated wafer was baked at 200° C. for 2 minutes to yield a 0.15 μmthick film with an optical density at 248 nm of 1.6.

The deep UV chemically amplified photoresist composition of Example 1was applied to the antireflective coated silicon wafer as a 1.0 μm thickcoating in the manner described in Example 1. The coated wafer wasimaged with a KrF laser (5mJ/cm²), subjected to a post exposure bake(PEB) at 90° C. for 90 seconds, and developed by immersion in 0.24NTMAH. The pattern was further transferred through the antireflectivecoating with O₂ RIE.

EXAMPLE 9

The lithographic performance of the deep- UV chemically amplifiedphotoresist composition of Example 1 comprisingpoly(p-hydroxy-styrene-co-p-t-butyloxycarbonyloxystyrene) andtrifluoromethylsulfonyloxybicyclo[2.2.1]-hept-5-ene-2,3-dicarboximide ina PM acetate casting solvent was evaluated over a number of substratesusing the crosslinked poly-(2-vinylnaphthalene)/DABMC antireflectivecoating of Example 4 compared to photoresist alone.

                  TABLE I                                                         ______________________________________                                        Substrate            Performance                                              ______________________________________                                        Silicon (HMDS).sup.1 flair                                                    Brewer CD-3.sup.2    occasional undercut                                      Brewer CD-5.sup.2    vertical profile                                         Brewer Omni-Layer.sup.2                                                                            severe footing                                           Hard-baked TNS.sup.3 severe footing                                           Hard-baked TNS.sup.3 vertical profile                                         (with antireflective coating)                                                 Silicon nitride      foot                                                     Silicon nitride      vertical profile                                         (with antireflective coating)                                                 Titanium nitride     severe footing                                           Titanium nitride     vertical profile                                         (with antireflective coating)                                                 Hard baked KTFR.sup.4                                                                              foot                                                     TEOS.sup.5           foot                                                     TEOS.sup.5           vertical profile                                         (with antireflective coating)                                                 ______________________________________                                         .sup.1 HMDS = hexamethyldisilazane                                            .sup.2 from Brewer Science, Inc.                                              .sup.3 TNS = a diazonaphthoquinone novolak resist                             .sup.4 KTFR = Kodak Thin Film Resist                                          .sup.5 TEOS = tetraethylorthosilicate                                    

Thus, it is apparent from Table 1 that lithographic processes using theantireflective coating of the invention are significantly improved bythe presence of the underlying antireflective layer.

EXAMPLE 10

Two sets of silicon wafers were used to show the benefits of theantireflective coatings of the invention. A control series of wafers wascoated with the deep UV chemically amplified photoresist shown inExample 1. The wafers were patterned with a Canon excimer stepper(0.37NA). All lines had a nominal width of 0.5 μm.

The line width variation with respect to film thickness is shown inTable II and is plotted as 1 in FIG. 2.

                  TABLE II                                                        ______________________________________                                        Film Thickness (Å)                                                                         Linewidth (μm)                                            ______________________________________                                        8183             0.47                                                         8352             0.41                                                         8635             0.53                                                         8886             0.45                                                         9342             0.55                                                         9822             0.48                                                         ______________________________________                                    

In a similar manner a set of wafers was first coated with 0.06 μm of theantireflective coating of Example 4 of the current invention using theprocessing conditions specified therein. Then the wafers were overcoated with chemically amplified deep UV photoresist as above. Theresults are shown in Table III and as 2 in FIG. 2.

                  TABLE III                                                       ______________________________________                                        Film Thickness (Å)                                                                         Linewidth (μm)                                            ______________________________________                                        8356             0.51                                                         8689             0.49                                                         8772             0.52                                                         9352             0.49                                                         9790             0.53                                                         9973             0.50                                                         ______________________________________                                    

It can be seen that the line width variations are greatly reduced byincluding the antireflective coating of the present invention in theprocessing.

EXAMPLE 11

Poly(bis-phenol-A)ethersulfone (Udel P1700/P3500 Resin, commerciallyavailable from Amoco Chemical, and Ultrason 1010, available from BASF)was dissolved in cyclohexanone to give a solution having 3% by weightsolids. The solution was applied to a silicon wafer having 5000 Å oxidelines patterned thereon by spin casting and the resulting film was bakedat 200° C. for 60 seconds. After baking, the antireflective film had athickness of about 1300 Å and an optical density of about 0.7 at awavelength of 248 nm. The deep-UV sensitive, chemically amplified resistcomposition of example 1 was applied to the antireflective coated wafer,and also to a control wafer having 5000 Å oxide lines over silicon butwithout the antireflective layer, to obtain 1.0 μm thick coatings in themanner described in example 1. Each resist coated wafer was patternwiseexposed to UV radiation from a KrF laser at a dose of 5 mJ/cm² thensubjected to a post exposure bake at 90° C. for 90 seconds to form alatent image. The latent image was developed by immersion in 0.24Naqueous tetramethyl ammonium hydroxide to form a relief image in thephotoresist. The relief image pattern was transferred into and throughthe antireflective layer by means of an O₂ reactive ion etching step.Etched resist over antireflective layer features consisting of lines andspaces having a 1.0 μm pitch and extending over 0.5 μm oxide steps wereexamined by SEM on the wafers with and without the antireflectivecoating. Electron micrographs of a section of each wafer are shown inFIGS. 3A and 3B. Without the antireflective underlayer, the images weredistorted. With the antireflective underlayer, straight walled images,free of reflective distortion were obtained.

EXAMPLE 12

A series of 17 antireflective coated silicon wafers were prepared byapplying and baking the antireflective composition of Example 11 usingthe method described to obtain a 1300 Å thick film on each wafer. Alayer of the chemically amplified photoresist composition of claim 1 wasthen applied to each wafer using a different spin speed for each waferto obtain overlying photoresist film thicknesses in the range from about7500 Å to about 9300 Å. A control series of wafers was prepared whereinthe photoresist of Example 1 was applied directly to the silicon waferwithout the antireflective layer, to give photoresist films havingthicknesses in a similar range. Using a standard reflectometer at awavelength of about 248 nm, the reflectance of each wafer was measured,to examine the reduction in reflectivity at 248 nm with theantireflective coating. As shown in FIG. 4, the chemically amplifiedresist of example 1 showed a reflectivity reduction upon the use of theantireflective coating of greater than 90%.

EXAMPLE 13

An antireflective composition was prepared consisting of a 2% by weightsolution in cyclopentanone of the imidized soluble polyimide derivedfrom the condensation reaction between a mixture of5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane and6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane with3,3',4,4'-benzophenone tetracarboxylic dianhydride (MATRIMID XU 218,commercially available from Ciba-Geigy). The composition was coated on asilicon wafer and then baked at about 180° C. for 2.0 min. The resultingantireflective film had a thickness of about 700 Å and had an opticaldensity of about 0.4 at a wavelength of about 248 nm. The positive tonechemically amplified photoresist of Example 1 was applied by spincoating over the antireflective film and subsequently baked to achieve aphotoresist film thickness of about 1.0 μm. The coated wafer waspatternwise exposed to UV radiation from a KrF excimer laser sourcehaving a wavelength of about 248 nm. The photoresist was then baked for1 min at about 90° C., and developed in 0.24N tetramethylammoniumhydroxide solution to form a relief structure in the resist. The reliefpattern was transferred into the underlying antireflective layer byoxygen reactive ion etching. A portion of the patterned and etched waferwas examined by scanning electron microscopy and the photoresist reliefstructures were observed to have straight and vertical side walls on topof the polyimide film with no protrusions or indentations at theinterface between the photoresist and antireflective layer films.

While the polymers disclosed herein are intrinsically UV radiationabsorbing, and the practitioner will appreciate that a separatechromophoric dye is not required, it will also be appreciated by theartisan that one or more dyes may be added to alternative embodiments toenhance certain optical properties of the antireflective coatingcompositions of the invention.

Although this invention has been described with respect to specificembodiments, the details thereof are not to be construed as limitations,for it will become apparent that various embodiments, changes andmodifications may be resorted to without departing from the spirit andscope thereof, and it is understood that such equivalent embodiments areintended to be included within the scope of this invention.

We claim:
 1. An antireflective coating composition for use withchemically amplified photoresist compositions comprising apoly(arylether) polymer, which is highly absorbent to mid and/or deep UVradiation, which is substantially inert to contact reactions with achemically amplified photoresist composition, and which is insoluble inthe developer for the chemically amplified photoresist composition.
 2. Aphotoresist structure having at least two layers and overlaying asemiconductor substrate comprisingan antireflective first layer coatedupon said substrate wherein the antireflective layer comprises apoly(arylether) polymer, and wherein the antireflective layer issubstantially inert to contact reactions with the photoresist layer, andwherein the antireflective layer is insoluble in the developer for thephotoresist layer, and a second layer coated upon said antireflectivefirst layer comprising a chemically amplified photoresist which issensitive to ultraviolet radiation having a wavelength in the range fromabout 180 nm to about 350 nm.
 3. The photoresist structure of claim 2wherein the antireflective first layer has an optical density of atleast 2.0/μm at the imaging wavelength of an overlaying photoresistlayer.
 4. The photoresist structure of claim 2 wherein theantireflective first layer has an absolute optical density of at least0.25 at the imaging wavelength of an overlaying photoresist layer. 5.The photoresist structure of claim 2 wherein the antireflective firstlayer has an optical density of at least 2.0/μm over the range ofwavelengths from about 235 nm to about 280 nm.
 6. The photoresiststructure of claim 2 wherein the antireflective first layer has anabsolute optical density of at least 0.25 over the range of wavelengthsfrom about 235 nm to about 280 nm.
 7. The photoresist structure of claim2 wherein the antireflective first layer is chemically non-reactive withthe photoresist second layer.
 8. The photoresist structure of claim 2wherein the antireflective first layer is immiscible with thephotoresist second layer.
 9. The photoresist structure of claim 2wherein the antireflective first layer is essentially insoluble inphotoresist casting solvents selected from the group consisting ofalcohols, esters, and ethers.
 10. The photoresist structure of claim 2wherein the poly(arylether) polymer is a poly(arylethersulfone).
 11. Thephotoresist structure of claim 10 wherein the poly(arylethersulfone) isa poly(bis-phenol-A)ethersulfone.
 12. The photoresist structure of claim2 wherein the antireflective first layer is obtained from a solution ofthe poly(arylether) polymer further comprising a cyclohexanone solvent.13. The photoresist structure of claim 2 wherein the poly(arylether)polymer itself absorbs UV radiation at the imaging wavelength.
 14. Thephotoresist structure of claim 2 wherein the antireflective first layeris further characterized by the absence of a dye component separate fromthe poly(arylether) polymer.
 15. The photoresist structure of claim 2wherein the antireflective first layer additionally comprises a dye. 16.A method of making a relief image by photolithography comprising thesteps of:applying, to a lithographic substrate, a layer of anantireflective coating composition for use with chemically amplifiedphotoresist compositions, wherein the antireflective coating compositioncomprises a poly(arylether) polymer which is highly absorbent to midand/or deep UV radiation, which is substantially inert to contactreactions with a chemically amplified photoresist composition, and whichis insoluble in the developer for the chemically amplified photoresistcomposition; and applying, over the antireflective coating composition,a layer of a chemically amplified photoresist composition; and exposingthe photoresist composition to form a latent image; and developing thelatent image to form a relief image pattern in the photoresist; and dryetching the relief image pattern into the antireflective coating layer.17. The method of claim 16 additionally comprising the step of heatingthe antireflective coating layer to a temperature in excess of the glasstransition temperature of the poly(arylether) polymer.
 18. The method ofclaim 16 wherein the poly(arylether) polymer is further characterized ashaving a glass transition temperature higher than the temperature towhich the chemically amplified photoresist is heated, and additionallycomprising the step of:after applying a layer of said chemicallyamplified photoresist composition, the step of heating the chemicallyamplified photoresist.
 19. The method of claim 18 additionallycomprising the step of: after exposing the photoresist composition toform a latent image, the step of heating the chemically amplifiedphotoresist.
 20. The method of claim 16 wherein the poly(arylether)polymer is further characterized as having a glass transitiontemperature higher than the temperature to which the chemicallyamplified photoresist is heated, and additionally comprising the stepof:after exposing the photoresist composition to form a latent image,the step of heating the chemically amplified photoresist.